EP0215431A2 - Verfahren zur Herstellung von Pyromellitsäuredianhydrid - Google Patents
Verfahren zur Herstellung von Pyromellitsäuredianhydrid Download PDFInfo
- Publication number
- EP0215431A2 EP0215431A2 EP86112478A EP86112478A EP0215431A2 EP 0215431 A2 EP0215431 A2 EP 0215431A2 EP 86112478 A EP86112478 A EP 86112478A EP 86112478 A EP86112478 A EP 86112478A EP 0215431 A2 EP0215431 A2 EP 0215431A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- dehydration
- temperature
- pyromellitic acid
- pyromellitic
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 38
- 230000018044 dehydration Effects 0.000 claims abstract description 31
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 208000005156 Dehydration Diseases 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000036555 skin type Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
Definitions
- This invention relates to a process for the preparation of high-quality pyromellitic dianhydride with a high efficiency by thermal dehydration of pyromellitic acid.
- pyromellitic dianhydride is used in various fields as a raw material for super thermal resistant resins. Its typical application is as electronic material.
- the sublimation purification process is not satisfactory due to the fact that thermal decomposition is liable to take place and the product is colored since the material is subjected to a relatively high temperature in this process.
- the process of using acetic anhydride has an advantage in that the material can be homogeneously heated.
- this process has disadvantages, since in the process, recovery of the solvent used is indispensable and it is difficult to eliminate the solvent completely from the product upon completion of the reaction.
- the process for conducting dehydration in a molten state is not advantageous since it needs a complicate apparatus and it results in deterioration and charring of the product.
- the process of dehydrating in a solid state is advantageous in that it does not require use of a solvent thus saving procedures for the solvent separation and recovery, and further that it is free from deterioration or decomposition of the compound as long as extremely high temperature is not used.
- the object of this invention is to provide a process for preparing pyromellitic dianhydride from pyromellitic acid by a simple way which can provide smoothly and rapidly the dianhydride with excellent quality and color.
- the characteristic feature of this invention is that in a process for preparing pyromellitic dianhydride by indirect heating of pyromellitic acid with a heating medium, when most of the pyromellitic acid was converted to the dianhydride, the remaining pyromellitic acid is dehydrated while regulating the tempereture of the heating medium between 200"C and 235°C.
- heating temperature is maintained at a high level, desirably above 240°C, since dehydration proceeds more efficiently when there is a larger temperature difference between solid pyromellitic acid and heating surfaces.
- a heating medium below the melting point of pyromellitic acid, i.e. between 240°C and 275°C.
- the temperature of the heating medium at this stage should be maintained between 200°C and 235°C, preferably between 220°C and 230°C.
- this invention relates to a process for preparing pyromellitic dianhydride by indirect heating of pyromellitic acid with a heating medium which comprises heating and dehydrating the pyromellitic acid while maintaining the temperature of the heating medium not lower than 240"C until most of the acid is converted to the dianhydride, and heating and dehydrating the remaining pyromellitic acid while regulating the temperature of the heating medium between 200°C and 235°C.
- any pyromellitic acid obtained by any process such as nitric acid oxidation, oxidation in an aqueous solvent or other liquid phase oxidation of durene can be used. Beside them any other pyromellitic acid may be used.
- those pyromellitic acids purified by means of purification treatment such as recrystallization from water are preferred.
- any kind of heating media generally in use may be employed.
- Preferred examples of such media include organic heating media such as Dowtherm, Mobiltherm, Marlotherm, diphenyl type heating medium, triphenyl type heating medium, Therm-S (Shin-nippon Seitetsu Kagaku-kogyo Co., Ltd.), KSK-oil (Developped by Kureha Kagaku Co., Ltd. and Sohken Kagaku Co., Ltd.), etc. and inorganic salts such as niter (mixture of NaNO z , KN0 3 and NaN0 3 ), etc.
- any type of apparatus may be suitably used so long as it is capable of heating solid material uniformly. They may be a fluidized bed type dryer equipped with indirect heating means, a paddle type dryer equipped with indirect heating means, a rotary type dryer equipped with indirect heating means, etc., wherein indirect heating means may be any type such as jacket, heating tubes, fin tubes, etc.
- the process of this invention can be carried out in batch-wise, semi-batch-wise or continuously. Dehydration may be carried out under normal pressure or either under increased or reduced pressure. In view of simplicity of the apparatus to be employed and efficiency of water removal from the system, however, normal or reduced pressure is preferred.
- an inert gas stream such as nitrogen gas, etc. into the dryer.
- pyromellitic dianhydride with a purity higher than 99 % can be produced with ease by regulating the temperature within a specific range at the final stage of dehydration. Further, by the process of this invention, pyromellitic dianhydride with excellent quality and color can easily, smoothly, and rapidly be formed in a form of free flowing particles.
- the process of this invention can be conducted in a very simple apparatus and a cheap material can be used for constructing the apparatus, since in the process of this invention, it is sufficient only to heat solid particles.
- a heating medium maintained at a temperature of 165°C had been circulated through the dryer in advance, and the rotor had been allowed to run at 35 rpm. Further, dry nitrogen gas had been kept to pass through the dryer at a rate of 2 Nm 3 /hr, so as to prevent the reverse reaction from occurring due to the water formed by the dehydration reaction.
- Pyromellitic dianhydride thus obtained was quite satisfactory in color, content of impurities and conversion, i.e. content of pyromellitic dianhydride.
- the amount of the recovered dianhydride was 193.4 kg, 95.7 % of the theoretical yield.
- Example 1 described above is given for the purpose to show a conventional process heretofore known in the art and not within the scope of this invention. Accordingly, Example 1 is a comparative Example.
- Example 2 Into the dryer used in Example 1, 216 kg of pyromellitic acid with neither free water nor water of crystallization was charged. The procedures followed were the same as those of Example 1, except that at the initial stage, the temperature of the heating medium was set at 270°C, and the temperature was changed to 240°C and 220°C when conversion has reached 70 % and 94.4 %, respectively. The results are shown in Table 2.
- Pyromellitic dianhydride thus obtained was quite satisfactory in color, content of impurities and conversion, i.e. content of pyromellitic dianhydride.
- the amount of the recovered dianhydride was 174.6 kg, 94 % of the theoretical yield.
- Example 3 Into the same dryer as used in Example 1, 236 kg of pyromellitic acid with neither free water nor water of crystllization was charged. Procedures for dehydration were similar to those of Example 1 except that the temperature of the heating medium was set at 240°C at the beginning of the dehydration reaction and the temperature of the heating medium was changed from 240°C to 225°C at the time when 80 % of conversion was achieved. The results are shown in Table 3.
- the amount of recovered pyromellitic dianhydride was 193.0 kg, 95 % of the theoretical yield. Pyromellitic dianhydride thus obtained was quite excellent in quality and color.
- the total hours to achieve conversion exceeding 99.5 % are about 30 hours in Example 1, about 7 hours in Example 2, and about 11 hours in Example 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60198467A JPH0676413B2 (ja) | 1985-09-10 | 1985-09-10 | 無水ピロメリツト酸の製造方法 |
JP198467/85 | 1985-09-10 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0215431A2 true EP0215431A2 (de) | 1987-03-25 |
EP0215431A3 EP0215431A3 (en) | 1988-09-21 |
EP0215431B1 EP0215431B1 (de) | 1990-11-28 |
Family
ID=16391589
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86112478A Expired EP0215431B1 (de) | 1985-09-10 | 1986-09-09 | Verfahren zur Herstellung von Pyromellitsäuredianhydrid |
Country Status (4)
Country | Link |
---|---|
US (1) | US4694089A (de) |
EP (1) | EP0215431B1 (de) |
JP (1) | JPH0676413B2 (de) |
DE (1) | DE3675860D1 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1066707C (zh) * | 1994-04-05 | 2001-06-06 | 株式会社日本触媒 | 生产1,2,4,5-苯四酸酐的方法 |
GB2348642B (en) * | 1998-07-31 | 2004-03-10 | Chinese Petroleum Corp | Process for the preparation of pyromellitic dianhydride |
JP4648515B2 (ja) * | 2000-05-02 | 2011-03-09 | 株式会社日本触媒 | 反応器のスタートアップ方法 |
US6579990B2 (en) | 2000-08-23 | 2003-06-17 | Mitsubishi Gas Chemical Company, Inc. | Process for producing refined pyromellitic acid and refined pyromellitic anhydride |
JP2002069073A (ja) * | 2000-08-23 | 2002-03-08 | Mitsubishi Gas Chem Co Inc | 高純度無水ピロメリット酸の製造方法 |
JP4626031B2 (ja) * | 2000-08-23 | 2011-02-02 | 三菱瓦斯化学株式会社 | 高純度ピロメリット酸および高純度無水ピロメリット酸の製造方法 |
JP2004217586A (ja) * | 2003-01-16 | 2004-08-05 | Mitsubishi Gas Chem Co Inc | 芳香族ポリカルボン酸及び該酸無水物の製造方法 |
JP4654632B2 (ja) * | 2004-08-18 | 2011-03-23 | 三菱瓦斯化学株式会社 | 無水ピロメリット酸の製造法 |
DE602006010626D1 (de) | 2005-07-21 | 2010-01-07 | Mitsubishi Gas Chemical Co | Verfahren zur Herstellung von hochreinem Pyromelliticdianhydrid |
JP5181436B2 (ja) * | 2005-07-21 | 2013-04-10 | 三菱瓦斯化学株式会社 | 高純度ピロメリット酸二無水物の製造法 |
CN102911181A (zh) * | 2012-11-14 | 2013-02-06 | 曹永平 | 一种高纯度均苯四甲酸二酐的制备方法 |
JP6789617B2 (ja) | 2015-06-25 | 2020-11-25 | キヤノン株式会社 | カルボン酸無水物の製造方法、カルボン酸イミドの製造方法および電子写真感光体の製造方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2151239A1 (de) * | 1971-04-26 | 1972-11-09 | Prolizenz Ag | Verfahren zur Dehydratisierung von Pyromellithsaeure |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2937189A (en) * | 1957-11-12 | 1960-05-17 | Du Pont | Production of pyromellitic dianhydride |
JPS4835253A (de) * | 1971-09-09 | 1973-05-24 | ||
FR2221574A1 (en) * | 1973-03-12 | 1974-10-11 | Protex Manuf Prod Chimiq | Shrink proofing and non-felting of wool - by treatment with known water-sol. cationic resins |
JPS5010572A (de) * | 1973-05-25 | 1975-02-03 |
-
1985
- 1985-09-10 JP JP60198467A patent/JPH0676413B2/ja not_active Expired - Lifetime
-
1986
- 1986-09-02 US US06/902,528 patent/US4694089A/en not_active Expired - Lifetime
- 1986-09-09 DE DE8686112478T patent/DE3675860D1/de not_active Expired - Lifetime
- 1986-09-09 EP EP86112478A patent/EP0215431B1/de not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2151239A1 (de) * | 1971-04-26 | 1972-11-09 | Prolizenz Ag | Verfahren zur Dehydratisierung von Pyromellithsaeure |
Also Published As
Publication number | Publication date |
---|---|
DE3675860D1 (de) | 1991-01-10 |
JPS6259280A (ja) | 1987-03-14 |
EP0215431B1 (de) | 1990-11-28 |
JPH0676413B2 (ja) | 1994-09-28 |
EP0215431A3 (en) | 1988-09-21 |
US4694089A (en) | 1987-09-15 |
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